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1,2-Addition of Formic or Oxalic Acid to –N{CH2CH2(PiPr2)}2 -Supported Mn(I) Dicarbonyl Complexes and the Manganese-Mediated Decomposition of Formic Acid

Journal Article · · Organometallics
 [1];  [1]
  1. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
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(PNHP)Mn(CO)2 (I) carboxylate complexes (PNHP = HN{CH2CH2(PiPr2)}2) were prepared in this study via 1,2-addition of either formic or oxalic acid to (PNP)Mn(CO)2 (PNP = the deprotonated, amide form of the ligand –N{CH2CH2(PiPr2)}2). The structural and spectral properties of these complexes were compared. The manganese formate complex was found to be dimeric in the solid state and monomeric in solution. Half an equivalent of oxalic acid was employed to form the bridging oxalate dimanganese complex. The catalytic competencies of the carboxylate complexes were assessed, and the formate complex was found to decompose formic acid catalytically. Both dehydrogenation and dehydration pathways were active as assessed by the presence of H2, CO2, and H2O. Lastly, the addition of LiBF4 exhibited a strong inhibitory effect on the catalysis.

Research Organization:
Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)
Sponsoring Organization:
USDOE; Laboratory Directed Research and Development (LDRD)
Grant/Contract Number:
89233218CNA000001
OSTI ID:
1483496
Report Number(s):
LA-UR--16-22530
Journal Information:
Organometallics, Journal Name: Organometallics Journal Issue: 12 Vol. 35; ISSN 0276-7333
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

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Cited By (22)

Synthesis and characterization of bis- and tris-carbonyl Mn(I) and Re(I) PNP pincer complexes journal October 2018
Manganese(I)-Catalyzed Cross-Coupling of Ketones and Secondary Alcohols with Primary Alcohols journal June 2019
Hydrogenation of Carbonyl Derivatives Catalysed by Manganese Complexes Bearing Bidentate Pyridinyl-Phosphine Ligands journal December 2017
A Highly Active Manganese Catalyst for Enantioselective Ketone and Ester Hydrogenation journal April 2017
Manganese(I)-Catalyzed Enantioselective Hydrogenation of Ketones Using a Defined Chiral PNP Pincer Ligand journal August 2017
Mangankomplexe in der (De)Hydrier-Katalyse - ein Vergleich mit Cobalt- und Eisenkatalysatoren journal December 2017
Manganese-Catalyzed Direct Olefination of Methyl-Substituted Heteroarenes with Primary Alcohols journal June 2018
A Highly Active Manganese Catalyst for Enantioselective Ketone and Ester Hydrogenation journal April 2017
Manganese-Catalyzed Sustainable Synthesis of Pyrroles from Alcohols and Amino Alcohols journal May 2017
Manganese(I)-Catalyzed Enantioselective Hydrogenation of Ketones Using a Defined Chiral PNP Pincer Ligand journal August 2017
Manganese Complexes for (De)Hydrogenation Catalysis: A Comparison to Cobalt and Iron Catalysts journal December 2017
Manganese-Catalyzed Direct Olefination of Methyl-Substituted Heteroarenes with Primary Alcohols journal June 2018
Oxidative Transformations of Biosourced Alcohols Catalyzed by Earth-Abundant Transition Metals journal June 2017
Highly Efficient Base-Free Dehydrogenation of Formic Acid at Low Temperature journal August 2018
Benyzl Alcohol Dehydrogenative Coupling Catalyzed by Defined Mn and Re PNP Pincer Complexes - A Computational Mechanistic Study: Benyzl Alcohol Dehydrogenative Coupling Catalyzed by Defined Mn and Re PNP Pincer Complexes - A Computational Mechanistic Study journal November 2018
Benzylene-linked [PNP] scaffolds and their cyclometalated zirconium and hafnium complexes journal January 2017
Carbon dioxide hydrogenation catalysed by well-defined Mn( i ) PNP pincer hydride complexes journal January 2017
Bio-mimetic self-assembled computationally designed catalysts of Mo and W for hydrogenation of CO 2 /dehydrogenation of HCOOH inspired by the active site of formate dehydrogenase journal January 2019
Catalytic upgrading of ethanol to n -butanol using an aliphatic Mn–PNP complex: theoretical insights into reaction mechanisms and product selectivity journal January 2019
Pentacarbonylmethylmanganese( i ) as a synthon for Mn( i ) pincer catalysts journal January 2019
Hydrogen production from formic acid catalyzed by a phosphine free manganese complex: investigation and mechanistic insights journal January 2020
A hemilabile manganese( i )–phenol complex and its coordination induced O–H bond weakening journal January 2020

Figures / Tables (7)

Figure 1(p. 2)figure Figure 1
Figure 2(p. 3)figure Figure 2
Figure 3(p. 3)figure Figure 3
Scheme 1(p. 3)figure Scheme 1
Scheme 2(p. 3)figure Scheme 2
Scheme 3(p. 4)figure Scheme 3
Table 1(p. 4)table Table 1

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY